New carbamoylalkyl phosphorus ester compounds



United States Patent Office 3,092,541 Patented June 4, 1963 3,092,541NEW CARBAMOYLALKYL PHOSPHORUS ESTER COMPOUNDS Ernst Beriger, Allschwil,Switzerland, assignor to Clba Limited, Basel, Switzerland, :1 company ofSwitzerland No Drawing. Filed Feb. 21, 1961, Ser. No. 90,636 Claimspriority, application Switzerland Feb. 24, 1960 11 Claims. (Cl. 167-42)This invention provides organic phosphorus compounds of the generalformula in which R represents a lower alkyl radical, and X represents anoxygen or sulfur atom.

The above compounds are new and are valuable agents for combating pests,especially harmful insects and acarids. They are active against thevarious stages of development, such as eggs, larvae and imagines, andthey are both contact poisons and stomach poisons.

The invention also provides a process for the manufacture of thecompounds of the above Formula I, wherein a compound of the formula Rr0(II) in which R, R, and X have the meanings given above,

and Me represents a cation, more especially an alkali metal ion, isreacted with a compound of the formula Hill-Br-C ON R, (III) in which RR and R have the meanings given above, and Hal represents a halogenatom, for example, bromine or chlorine.

The compounds of the general Formula II are advantageously dialkylesters of dithio phosphoric acid or of thiolphosphoric acid, of whichthe alkyl radical contain 1 to 4 carbon atoms, and also alkali metalsalts of these esters.

The compounds of the general Formula (III) are hydroxylamides, forexample, OzNadialkyl-hydroxylamides, of lower monohalogenatedmonocarboxylic acids.

The reaction components are reacted at the ordinary or a raisedtemperature, for example, at a temperature within the range of 0 to 120C., and advantageously 10 C. to C. It may be of advantage or convenientto work in an inert solvent, such as an alcohol or a ketone, forexample, acetone or methanol or to add water and, if desired, to work inan atmosphere of an inert gas, for example, under nitrogen, and/ orunder reduced pressure.

It may also be of advantage to react the aforesaid starting materialswith the aid of heat in a two-phase system which consists, for example,of water and an organic solvent, for example, methylene chloride, therelative proportions of the aqueous or organic phase varying withinrelatively Wide limits.

As stated above, the compounds of the invention are valuable agents forcombating pests, especially insects and acarids.

Accordingly, the invention also provides pest combating preparationswhich comprise an active substance of the above Formula I in admixturewith a liquid or solid diluent.

A very wide variety of materials or objects can be protected againstpests, including harmful insects and acarids, and a gaseous or liquid orsolid substance may be used as a carrier for the active substance. Assuch substances ,to be protected or to be used as carriers there may bementioned, for example, air, especially in rooms, and liquids, forexample, water in ponds and finally any dead or living solid substratum,for example, objects in living rooms, cellars, attics or stables, andalso pelts, feathers, wool or the like, and also living organisms of thevegetable or animal kingdom in their very wide variety of stages ofdevelopment, provided that they are not sensitive to the pest combatingagents.

The combating of pests is carried out by the usual methods, for example,by treating the material or object to be protected with the activecompound in the form of vapour, for example, as a fumigant, or in theform of a dusting or spraying preparation, for example, as a solution orsuspension, which may be prepared with water or an organic solvent, forexample, alcohol, petroleum, a tar distillate or the like. Thepreparations may also be in the form of aqueous solutions or aqueousemulsions of organic solvents which contain active substances, and whichemulsions or solutions can be applied to the objects or materials to beprotected by brushing, spraying or dipping.

The spraying or dusting preparations may contain the usual inert fillersor marking agents, for example, kaolin, gypsum or bentonite, or otheradditions such as sulfite cellulose waste liquor, cellulose derivativesor the like, and they may also contain the usual wetting agents oradherent agents for improving the wetting capacity or adherent propertyof the preparations. The pest combating preparations may he made up inpowder form, in the form of aqueous dispersions or pastes, or in theform of self-dispersing oils.

A compound of the Formula I may be the sole active substance present inthe preparation or it may be present in combination with anotherinsecticide and/ or fungicide.

Such preparations are used for plant protection by the usual spraying,pouring, dusting or fumigating methods.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated, and therelationship of parts by weight to parts by volume being the same asthat of the kilogram to the liter.

EXAMPLE 1 A solution of 19.8 parts of the sodium salt ofdimethyldithiophosphoric acid in 40 parts by volume of acetone istreated within minutes dropwise with a solution of 13.75 parts ofchloroacetic acid-O:N-dimethylhydroxylamide (melting at 41 C.) in 20parts by volume of acetone. The reaction is slightly exothermic. Themixture is stirred for one hour at room temperature and then for 2 hoursat 40 to 45 C., the precipitated sodium chloride is filtered off and thefiltrate is evaporated in vacuo at 40 C. The residue is taken up in 50parts by volume of methylene chloride and washed with parts by volume ofwater and then with 2X10 parts by volume of sodium bicarbonate solution.The solution is dried over sodium sulfate and evaporated in vacuo, toyield as residue 20.55 parts of a compound of the formulaAnalysis.-Calculated: P, 11.95%. Found: P, 11.8%.

EXAMPLE 2 As described in Example 1, 22.9 parts of the sodium salt ofdiethyldithiophosphoric acid are reacted with 13.75 parts ofchloroacetic acid-O:N-dimethylhydroxylamide, to yield 23.5 parts of acompound of the formula Analysis-Calculated: P, 10.78%. Found: P, 10.6%.

EXAMPLE 3 As described in Example 1, 9.9 parts of the sodium salt ofdimethyldithiophosphoric acid are reacted with 8.25 parts ofchloroacetic acid-O-methyl-N-isopropylhydroxylamide (boiling at 55 to 59C. under a pressure of 0.08 mm. Hg), to yield 9.7 parts of a compound ofthe formula S all-10 (CH O)a1 L -SCH CON0CH| Analysis.-Calculated: P,10.78%. Found: P, 11.2%.

EXAMPLE 4 Analysis.-Calculated: P, 9.82%. Found: P, 9.8%.

(b) As described in Example 1, 10.95 parts of chloroacetohydroxamic acidin 25 parts by volume of acetone are reacted with 19.8 parts of thesodium salt of dimethyldithiophosphoric acid by being stirred for 20hours at room temperature. There are obtained parts of a compound of theformula (OH:O)z I SCHICOI q-OH vinalysis.-Calculated: P, 13.40%. Found:P, 13.41%.

4 EXAMPLE 5 22.4 parts of the sodium salt of dimethyldithiophosphoricacid are stirred with a solution of 12.8 parts of chloroaceticacid-N-methoxyamide (melting at 41 C.) in 45 parts by volume of water.The temperature is maintained for 7 hours at 10 to 15 C., whereupon themixture is stirred for another 24 hours at room temperature. The oil isisolated and the aqueous solution is washed with 50 parts by volume ofbenzene. The benzene solution is combined with the oil, washed with asmall amount of sodium bicarbonate solution and dried over sodiumsulfate. The benzene is evaporated in vacuo at a bath temperature of 40to 50 C., to yield as residue 16.4 parts of a crystalline compound ofthe formula 8 II I (CHlOhP-SCILCON-O 0H,

melting at 47 to 48 C.

Analysis-Calculated: P, 12.63%. Found: P, 13.0%.

EXAMPLE 6 As described in Example 5, 23.8 parts of the sodium salt ofdiethyldithiophosphoric acid are reacted with 11.8 parts of chloroaceticacid-N-methoxyamide, to yield 22.8

parts of a compound of the formula 1 Analysir.Calculated: P, 11.34%.Found: P, 11.4%.

EXAMPLE 7 which on recrystallization from benzene forms white needlesmelting at 67 C.

AnaIysis.--Calculated: P, 12.63%. Found: P, 12.7%.

EXAMPLE 8 (a) A solution of 12.35 parts of chloroacetic acid-N-methylhydroxylamide and 22.9 parts of the sodium salt ofdiethyldithiophosphoric acid in 30 parts by volume of water is heated to30 C. The heating is then discontinued and the mixture is stirredovernight at room temperature. The oil which forms is separated fromwater. The water is washed with 50 parts by volume of methylenechloride, the oil is combined with the methylene chloride extract andthe whole is agitated with 10 parts by volume of saturated sodiumbicarbonate solution. The solution is dried over sodium sulfate andevaporated in vacuo at 40 to 50 C., to yield as residue 24.8 parts of acompound of the formula 1 7 tHlohh-scnrcoN-on Analysis.-Calculated: P,11.33%. Found: P, 11.28%.

(b) When the salts of the esters of dithiophosphoric acid are reacted asdescribed above with the hydroxylamides shown in the following Table I,the compounds 1 to 12 of the Table I are obtained:

' Table I Ogmp. Esteroldlthllgphosphorlc Hydroxylamlde Formulae! flnalproduct Analjsis i 02H; 5 01H; 1 (GHaO):P-S-Na G10Hr-O0N\ (OH )|1'SOHrO0N\ ififiihlffig.

on 0H (31K; 3 C135 2 0,H,o),r-s-Na. ClOHr-CO-N\ (O:H 0)|PSOHzO0N\ iigg g-g gg igfi;

on OH H 01H: '8' 0111i 3 (0H O]sPS-Na C1OH:CO--N oH.o),PscH,-coN.333335%;

OCQHI OCIH| S CsH; 1? 01B: 4 (C;H O):1 SNa ClOHr-CO-N (CgH OhP-S-CHg-OON001115 002 1 OH| S /CH: 50:- (CH;O)gP-SNa Br-OHxCHr-GO-N (cmmd-s-cur-cflr-oo-N ffi g? 0011, 00H. OH! /CH; 3 CH: /CH. 5 (CH O);P-SNaBr-oH-oo-N omo),P-s-oH-c0-N fi 3 fii,

00m 0011. H on, /0H| s 0H, 0H, 1 o.H.o .P-s-Na Br( 3H-C0N (cmlo),r-s-on-oon gag- 3 33 n 01B: S! 01111 8 wmonr-s-m C1-CH CO-N\(0H|0)|1-8OHr0ON gfg g fig OH OH 3 03H1 (ISO) 7 7 :5 0,117 (150) 9 mmmd-s-Na Cl-OHrC0N\ o,mo)n -s-cm0o-N ggg g ggg g OH OH CHaO 8 /CH5 01130 8/CH;

P calm: 10.787. -s-K cl-om-oo N P-S orb-co N Round: 9%?

(OH!)ICHO OCH| (CHIJIOHO OCH;

CHgO S 1 /CH1 7 GHaO S /GH| n SK. cu-om-oo-n 1LSCH:CO-N g? 9 i OllIld-83%.

oH.o s /CH; on.o e on.

Peale; 11.3397. 12 P S-K.-- o1 cH.-co N\ 1 s orb-c0 N Hound: 113360.

ommno on rorm mno v 7 0H EXAMPLE 9 55 Analysis.Calcu1e.ted: P, 10.94%.Found: P, 11.02%. (a) A solution of 39.8 parts of the potassium salt ofA Solution of W of the 1101355111111 5311 of dimethylthiolphosphoricacid and 27.5 parts of chloro- Y P P acid P8118 of 6111011 aceticacid-O:N-dimethylhydroxylamide in 60 parts by whoac1d-N-mehy1hydr0xy1anude m 30 parts y volume of acetone is heated for 8hours at 40 to C. i acetone 18 hqawd r 8 hours at 40 to 50 C. Afterworking up as described in Example 1, followed Workmg P as described 111Example 1 Ylelds P by distillation in a high vacuum, there are obtained25.2, of the compound 0f the formula parts of the compound of theformula 0 Elm E I JJ -SOHqCONwOH; I HaOONOH boiling at 131 to 135 C.under 0.12 mm. Hg pressure. Analysis.Calcu1ated: P, 13.52%. Found: P,13.4%. Analysis.-Ca1culated: S, 13.18%. Found: S, 13.0%. (d) A mixtureof 229 parts of the potassium salt of A Solution of 2239 P8115 0f thePotassium Salt 0f diethylthiolphosphoric acid and 12.35 parts ofchlorodielhylthiolphosphol'ic acid and P8118 0f ChlOfO- aceticacid-N-methylhydroxylamide in 30 parts by volume wtic i i y y y i 30 P my of acetone is heated for 18 hours at 40 to 50 C. Working volume ofacetone is heated for 8 hours at 40 to 50" C. up as described in Example1 yields 17.1 parts of a com- Working up as described in Example 1yields 14.4 parts of pound of h f l the compound of the formula boilingat 155 to 159 C. under 0.2 mm. Hg pressure. Analysis,--Oa.lculated: P,12.04%. Found: P, 12.0%.

7 EXAMPLE 10 (a) As described in Example 8, 16.55 parts of chloroaceticacid-N-methyl-N-acetoxyamide are reacted with 19.8 parts of the sodiumsalt of dimethyldithiophosphoric used as a liquid spray concentratewhich can be emulsified by being poured into water.

(A) To determine the contact effect of this product on aphids thefollowing experiment was conducted with the acid in 30 parts of waterand parts by volume of acetone 5 use of liquid Sprays containing.mspectively 0'04% by being stirred for 16 hours at room temperature.There %fig iigag zi gg ggz gigggg f' with aphids are Obtained parts of agi of the formula were sprayed all over and after 48 hours the eifectachieved was determined. When a 100% effect was observed, the0HaC0N-0C0011: plants were infested with fresh aphids and the effectagain \A i 1 t d; P, 10 73%, F d; P 1031 73, checked after another 48hours. The results so obtained (b) As described in Example 8, 16.55parts of chlor are summarized in the following Tables II and III. aceticacid-N-methyl-N-acetoxyamide are reacted with each P an Identifying markwas used! 22.08 parts of the sodium salt of diethyldithiophosphoricsignifies that no live aphids were left; acid in parts of water and 5parts by volume of ace- 15 signifies insufiicient or no effect; tone bybeing stirred for 16 hours at room temperature. signifies good efiect,only few live aphids left.

Table II Cone. of Ex. 8(b) Ex. 8(b) Ex. 8(bl active Table I Table ITable I subst. in Ex. 1 Ex. 2 131.3 Ex. 4(a) Ex. 7 Ex. 8(a) Comp. Comp.Comp. Ex. 9(a) Ex. 9(b) spray liquid, N0. 1 N0. 3 No. 4

percent 4-+ 4-4- +4- +4 +4- 4-4- -l--l- +4. t

Table III Effect on aphids 48 hours after relntestatlon Cone. of activeprinciplein Ex.8(b) Ex.8(b) Ex. Btb) spray liquid, Ex. 1 131.2 Ex. 3 Ex.4(a) Ex. 7 Ex. 8(a) Table I Table I Table I Ex. 9(a) Ex. 9(b) percentComp. Comp. Comp.

N o. 1 No 3 No 4 1': J5 l I I I 1 There are obtained 29.4 parts of thecompound of the formula A mixture of 13.75 parts of chloroaceticacid-OzN-dimethylhydroxylamide and 30.8 parts of the potassium salt ofbismethoxy-ethyldithiophosphoric acid are stir-red for (B) To determinethe effect on aphids by diffusion through the leaves the followingexperiment was conducted with the use of liquid sprays containingrespectively 0.08%, 0.04%, 0.02% and 0.01% of active prineiple.

Of the broad beans which were infested with aphids only on the undersideof the leaves, only the upper surface of the leaves was sprayed with theliquid sprays described above and after 48 hours the etfect on theunderside of the leaves was inspected. The results oh- 4 hours at theboil in the two-phase system water (120 0 tained are summarized in thefollowing Table IV:

Table IV Eiiect on aphids by diflusion Conoentr. of active principle inspray liquid, percent Ex. 8(b) Ex. 8(b) Ex. 1 Ex. 2 Table I Table I Ex.9(a) Ex. 9(b) Ex. 9(0) Ex. 9(d) comp. No 7 comp. N010 parts by volume):methylene chloride (40 parts by volume). Working up as described inExample 8 yields 29.0 parts of a compound of the formula(OHtoCIH40)$"SCH:GO]1I-OCH; Analysis-Calculated: P, 8.92%. Found: P,8.42%.

EXAMPLE l2 2 parts each of the condensation products of Examples 1 to 11are mixed with 1 part of the condensation product from 1 molecularproportion of tertiary octylphenol and 8 molecular proportions ofethylene oxide and 7 parts of isopropanol. The resulting clear solutioncan be The results are shown in the following Table V:

Table V Effect on red spider mite Compound Check Check b Example 3 4m E4(1)) l 1E 7 Example 8(a) l Ex. 80)) Table I, Comp. 1..-..- Ex. 8(b)Table I, Comp. 2- Ex. 80:) Table 1, Comp. 3. Ex. 80;) Table I, Comp. 4.EX. 8(b) Table I, Comp. 5- I I Ex. 80)) Table I, Comp 8- Ex. 801; TableI, Comp. 9 Ex. 80) Table 1, Comp. l1--. I

Ex. 80)) Table 1, Comp. 12 I Example 11 I No'rn.- signifies: All redspider mites destroyed, signines: Good acaricidal eflfect; only fewspider mites left a we.

The compounds of Examples 1 to 11 further have a good t very goodstomach poison efiect on Musca domestica, Carausius morosus, Orgyiagonostigma and Gastroidea viridula.

To manufacture liquid spray concentrates there may also be used wettingand emulsifying agents other than those mentioned above.

There may be used non-ionic products, for example condensation productsof aliphatic alcohols, amines or carboxylic acids containing a longchain hydrocarbon radical of about to 30 carbon atoms with ethyleneoxide, such as the condensation product from: Octadecyl alcohol with 25to '30 mols of ethylene oxide, or soybean fatty acid with 30 mols ofethylene oxide, or commercial olcylamine with mols of ethylene oxide, ordodecylmeroaptan with 12 mols of ethylene oxide.

As suitable anionic emulsifiers there may be mentioned: the sodium saltof dodecyl alcohol sulfuric acid ester, the sodium salt ofdodecylbenzenesultonic acid, the potassium or tricthanolarnine salt ofoleic or abietic acid or of mixtures of these acids, and the sodium saltof a petroleum-sulfonic acid.

Instead of with isopropanol the liquid spray concentrates may beprepared with other solvents, for example ethanol, methanol, butanol,acetone, methylethyl ketone, methylcyclohexanol, benzene, toluene,xylene, kerosenes, or petroleum fractions. Likewise suitable aremixtures of difierent solvents.

EXAMPLE l3 2 parts each of the condensation products of Examples 1 to 11are mixed with 9 parts of chalk and 1 part of wetting agent. A dustingpowder is obtained from which liquid sprays can be prepared bysuspension in water. When the walls of stables are treated with such aspray containing 0.04% of active principle, good effects against fliesand midges are obtained.

What is claimed is:

1. An organic phosphorus compound of the formula in which R and R, eachrepresents an alkyl radical containing at most 4 carbon atoms, m, n andp each represents a whole number of at the most 2, and x and y eachrepresents a whole number of at the most 4.

2. An organic phosphorus compound of the formula R-O o P-som o o cnny LJp-l Rr-O in which R and R each represents an alkyl radical containingat most 4 carbon atoms, m, n and p each represents a whole number of atthe most 2, and x and y each represents a whole number of at the most 4.

3. An organic phosphorus compound of the formula in which R, R and Reach represents an alkyl radical containing at most 4 carbon atoms and mand p each represents a whole number of at the most 2, and x and y eachrepresents a whole number of at the most 4.

4. An organic phosphorus compound of the formula in which R, R and Reach represents an alkyl radical containing at most 4 carbon atoms and mand ,0 each represents a whole number of at the most 2, and x and y eachrepresents a whole number of at the most 4.

5. An organic phosphorus compound of the formula in which R, R and Reach represents an alkyl radical containing at most 4 carbon atoms and mand n each represents a whole number of at the most 2 and x and y eachrepresents a whole number of at the most 4.

7. An organic phosphorus compound of the formula in which R representsan alkyl radical containing at most 4 carbon atoms, R represents acyclohexyl radical, and m, n and p each represents a whole number of atthe most 2 and x and y each represents a whole number of at the most 4.

8. An organic phosphorus compound of the formula in which R representsan alkyl radical containing at most 4 carbon atoms, R represents acyclohexyl radical, and m, n and p each represents a Whole number of atthe most 2 and x and y each represents a whole number of at the most 4.

9. The compound of the formula S OH: (CHiO):i SCH;OOI IO H. 10. Thecompound of the formula CH; (CII;O)zl -SCH;-COI I0H 11. The compound ofthe formula CH, (CaHsO):ii-SCH:=CONOCH; 12. The compound of the formulas 0H, :Hr0): I S--( JHC0N 00H, 13. The compound of the formula 0 CH:(0Ht0):i s-0H,coN

OCH;

14. The compound of the formula 0 CH| 1H|O):i -S-CHrCO-N 00H, 15. Anorganic phosphorus compound of the formula R-o o P-S-R4-O Relwherein Rrepresents an alkyl radical containing at most 4 carbon atoms, Rrepresents a member selected from the group consisting of a hydrogenatom and an alkyl radical containing at most 4 carbon atoms, Rrepresents a member selected from the group consisting of the group -CHthe group -CH CH and the group in which R, represents an alkyl radicalcontaining at most 4 carbon atoms, and X represents a member selectedfrom the group consisting of an oxygen atom and a sulfur atom.

16. A preparation for combating pests which comprises an organicphosphorus compound of the formula in which R, R to R and X have themeanings given in claim 15.

References Cited in the file of this patent UNITED STATES PATENTS2,959,608 Crouch et a1 Nov. 8, 1960 FOREIGN PATENTS 663,270 GreatBritain Dec. 19, 1951 791,824 Great Britain Mar. 12, 1958

15. AN ORGANIC PHOSPHORUS COMPOUND OF THE FORMULA